This invention concerns highly crystalline propylene polymers, and cast laminates produced from them. Moreover, it concerns a process for the production of said laminates from said polymers.
The polymers of this invention make it possible for the laminates produced from them by way of the process of the present invention to have good optical qualities, particularly transparency and gloss, although maintaining, even at elevated temperatures, high mechanical properties, such as stiffness, that are typical of highly crystalline polypropylene. By virtue of the above mentioned characteristics and low percentage of solubility in xylene due to the high crystallinity of the polymers used, the laminates of this invention are particularly suitable for packaging food products.
Propylene polymers for the production of films with good transparency and high mechanical properties are already known. Said films are described, for example, in European patent EP 497590. According to said patent, the characteristics mentioned above are obtained by using highly crystalline polypropylene with a melt flow rate (MFR) ranging from 1 to 10 dg/min, and a ratio between weight average molecular weight ({overscore (M)}w) and number average molecular weight ({overscore (M)}n), i.e., {overscore (M)}w/{overscore (M)}n, ranging from 2.5 to 4.
Now it has surprisingly been found that it is possible to obtain cast laminates having both good transparency and good mechanical properties even by using propylene polymers with parameters outside those indicated in the above mentioned patent.
Thanks to the polymers of the present invention it is possible to produce laminates that at equal thickness possess good mechanical properties and even more transparency when compared to those obtained with polymers of the known art.
As mentioned above, said laminates also present an excellent gloss.
Therefore, this invention provides propylene crystalline polymers having:
(a) MFR ranging from 5 to 15 g/10 min, preferably from 6 to 13, more preferably from 9 to 12;
(b) ratio between weight average molecular weight ({overscore (M)}w) and number average molecular weight ({overscore (M)}n), i.e., {overscore (M)}w/{overscore (M)}n, ranging from 4.5 to 9, preferably from 5 to 8, more preferably from 6 to 8;
(c) polydispersity index (PI), measured with the method described below, ranging from 2 to 6, preferably from 3 to 5;
(d) density equal or greater than 0.9020 g/cm3; and
(e) solubility in xylene at ambient temperature, i.e., at about 25xc2x0 C., not greater than 2.5% by weight, preferably not greater than 2%;
said polymers can be obtained by way of chemical visbreaking of a polymer having a polydispersity index ranging from 5 to 8, preferably from 6 to 7.
The polymers of this invention are selected from propylene homopolymers, which are preferred, and copolymers of propylene with ethylene or a C4-C8 xcex1-olefin, or their mixtures; mixtures of homopolypropylene and the above mentioned copolymers can also be used. The above mentioned xcex1-olefins, that can be linear or branched, are preferably selected from 1-butene, 1-hexene, and 3-methyl-1 -pentene. The quantity of ethylene in the copolymers does not exceed 1% in moles, while the quantity of C4-C8 xcex1-olefin varies, for example, from 0.2 to 5% in moles, more preferably from 0.2 to 1%.
The polymers of the present invention are prepared in one or more polymerization stages using, among the known Ziegler-Natta catalysts, those that are highly stereospecific. In particular, the catalyst system used comprises (a) a solid catalytic component that comprises a titanium compound, and an electron-donor compound, both are supported on magnesium chloride, and (b) an Al-trialkyl compound and an electron-donor compound.
Examples of catalysts and polymerization processes that can be used are described in published European patent application EP-A-45977.
Therefore, this invention provides propylene crystalline polymers having:
(a) MFR ranging from 5 to 15 g/10 min, preferably 6 to 13, more preferably from 9 to 12;
(b) ratio between weight average molecular weight (Mw) and number average molecular weight (Mn), i.e., Mw/Mn, ranging from 4.5 to 9, preferably from 5 to 8, more preferably from 6 to 8;
(c) polydispersity index (PI), measured with the method described below, ranging from 2 to 6, preferably from 3 to 5;
(d) density equal or greater than 0.9020 g/cm3; and
(e) solubility in xylene at ambient temperature, i.e., at about 25xc2x0 C., not greater than 2.5% by weight, preferably not greater than 2%;
said polymer being obtained by way of chemical visbreaking of a polymer having a polydispersity index ranging from 5 to 8, preferably from 6 to 7.
The usual additives, such as stabilizers and pigments, can be added to the polymers of this invention. In the production of laminates, the usual additives which are added are those specific to said sector, i.e., antiblocking (such as silica), and slip agents, such as erucamide. An additional object of this invention are the cast laminates prepared from the above mentioned polymers, having the optical and mechanical properties mentioned above. Said laminates, where the term is used to describe film and sheets, have a thickness ranging from 0.01 mm to 0.5 mm, typically from 0.01 to 0.4 mm.
The laminates of the present invention can be mono-layered or multi-layered. In the case of the latter, at least one layer consists of,a polymer of this invention.
Generally speaking, the laminates of the present invention do not present fish eyes with dimensions greater than 1.5 mm, determined with the method described below. Typically, the number of fish eyes per square meter having dimensions ranging from 0.7 mm to 1.5 mm is not greater than 3, and there are no more than 300 fish eyes per square meter with dimensions ranging from 0.2 to less than 0.7 mm.
In order to obtain laminates having the above mentioned properties, the polymers undergo a lamination process which includes subjecting the laminate that has just been produced and is still hot, at the exit of the die for example, to immediate cooling to room temperature or even less, for example equal to or lower than 20xc2x0 C., preferably lower than 15xc2x0 C. Said cooling occurs in no more than 2 seconds, preferably 1.9 seconds.
A typical lamination process according to this invention comprises:
1) subjecting to extrusion and lamination the above mentioned propylene polymers; and consecutively
2) subjecting the laminate exiting the die of the extruder to a rapid cooling (quenching) until the surface of the laminate is cooled to a temperature not higher than 70xc2x0 C. in a period of time not greater than 2 minutes.
The quenching of the laminate can occur in various ways: for example, by putting the laminate in contact with a surface, such as that of a rotating roller, maintained at a temperature lower than 20xc2x0 C., preferably not higher than 15xc2x0 C.
As an example of the process of this invention, the quenching of a 0.05 mm thick film starts 0.07-0.13 seconds after the film exits the die.
The extrusion of the polymers occurs by using conventional extrusion technologies and apparatus (for example a Bandera extruder), as well as operating conditions. Generally speaking, the laminate exiting the die of the extruder is conveyed to a roller whose surface temperature is maintained within the range mentioned above.
The following examples are given in order to illustrate, but not limit the present invention. Tests have been carried out on the polymer and film of this invention in order to evaluate their characteristics and properties; the methodology used to conduct said tests is described below.
Solubility: determined as the percentage of residue soluble in xylene at 25xc2x0 C. in the following manner: one prepares a solution of the sample in xylene at a concentration of 1% by weight stirring the sample for one hour in xylene at 135xc2x0 C. While still stirring, the solution is allowed to cool to 95xc2x0 C., after which it is poured into a 25xc2x0 C. bath where it is kept for 20 minutes without stirring, then the stirring is resumed for an additional 10 minutes. The solution is then filtered, and acetone is added to a portion of the filtrate in order to obtain the precipitation of the dissolved polymer. The polymer thus obtained is recovered, washed, dried, and finally weighed to determine the percentage soluble in xylene.
Melt Flow Rate (MFR): according to method ASTM-D 1238, condition L.
Polydispersity Index (PI): calculated by way of a dynamic test carried out with a RMS-800 rheometric mechanical spectrometer. The PI is defined by the equation PI=105/Gc, where the Gc (crossover modulus) value is the one where Gxe2x80x2 (storage modulus) coincides with Gxe2x80x3 (loss modulus). A sample is prepared with one gram of polymer, said sample having a thickness of 3 mm and a diameter of 25 mm; it is then placed in the above mentioned apparatus and the temperature is then gradually increased until it reaches a temperature of 200xc2x0 C. after 90 minutes. At this temperature one carries out the test where Gxe2x80x2 and Gxe2x80x3 are measured in function of the frequency.
Flexural modulus of elasticity: ASTM D-790
Gel content: the number of fish eyes per square meter of a film 0.05 mm thick is determined by automatic count with an optic counter using the Sistemi Intelligenti sipar apparatus.
Haze: ASTM D-1003
Gloss: ASTM D-2457
Friction coefficient: ASTM D-1894, Condition D. The test is carried out on a laminate at 23xc2x0 C. 24 hours after the extrusion. According to this method, in order to determine the friction coefficient (FC) the laminate is caused to slide on a metallic guide prepared according to method DIN 4768.